KR20140038560A - Surface-treated calcium carbonate for binding and bioremediating hydrocarbon-containing compositions - Google Patents

Abstract

The present invention relates to the use of surface treated calcium carbonate for bonding and biopurifying a hydrocarbon-containing composition, a method for bonding and biopurifying a hydrocarbon-containing composition, as well as the use of surface-treated calcium carbonate for bonding and biopurifying a hydrocarbon-containing composition, And a surface-treated calcium carbonate and a hydrocarbon-containing composition.

Description

SURFACE-TREATED CALCIUM CARBONATE FOR BINDING AND BIOREMEDIATING HYDROCARBON-CONTAINING COMPOSITIONS

The present invention relates to a surface treated calcium carbonate for binding and bioremediating a hydrocarbon containing composition, a method for bonding and biopurifying a hydrocarbon containing composition, as well as a surface treated calcium carbonate for binding and biopurifying a hydrocarbon containing composition. And to composite materials containing surface treated calcium carbonate and hydrocarbon containing compositions.

Contamination of soil, seawater or groundwater with water insoluble fluids, such as compositions comprising hydrocarbons, poses serious environmental problems throughout the world. In this regard, hydrocarbon containing compositions such as crude oil contribute significantly to the contamination of seawater and soil, while refined petroleum products such as gasoline, aviation fuel, diesel fuel and other refined petroleum products are the most common groundwater and soil. It is a pollutant. In particular, oil spills, including the release of crude oil from tankers, offshore structures, drilling rigs and oil wells, as well as the outflow of heavy fuels used by refined petroleum products and large vessels, such as bunker fuels, or oily waste or waste oil Outflow is becoming an increasing problem.

In the art, several methods have been proposed for restoring hydrocarbon contaminated media such as soil, groundwater, seawater and coastline. For example, in the case of water contaminated with hydrocarbons, one method involves adding a precipitant in the form of an emulsifier and a dispersant to bind a water insoluble fluid such as crude oil and to maintain a mixture of precipitant and crude oil suspended in seawater. do. For example, British Patent No. 353 945 converts a petroleum product into a biodegradable emulsion, comprising contacting the petroleum product with an emulsion composition comprising water and the following components and mixing the components to form an emulsion. A) 15 to 80 parts by weight of microbial nutrients comprising molasses, cellulose, sugarcane waste, casein, malt extract, proteases, ammonium salts, amines, amides and / or fermented dregs, b) alkalis Or alkaline earth metal salts and reducing surface tension comprising calcium silicate, sodium silicate, potassium silicate, calcium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, dibasic sodium phosphate, dicalcium phosphate, and / or monobasic or dibasic ammonium phosphate 10 to 50 parts by weight of the component, and c) a diluent. EP 0 617 991 A1 refers to a method for recovering oil from waste oil fluids and removing oil from industrial waste water using water-soluble polymers dispersed in a concentrated salt medium. US Patent Application Publication 2006/032820 A1 discloses a solid borehole material, such as a drill cutting or water, such as underground, comprising contacting a solid material / water with an amino substituted polymer such as chitosan and a halogenating agent. Described are methods for removing oil from water produced by formation. British Patent 1,192,063 forms agglomerates of said powders and said oils or oil derivatives having a specific gravity higher than that of water by applying mineral powders treated to be hydrophobic or higher hydrophobic to oils or oil derivatives and A method of treating contaminated water with an oil or an oil derivative on its surface, comprising the step of precipitation through.

In medium, such as seawater, this method has the advantage that by suspending a mixture of precipitant and oil in water, oil, for example oil from an oil spill, is removed relatively quickly from the water surface, thus significantly preventing hydrocarbon contamination of adjacent shorelines. Has

However, this method results in a suspension of mixtures comprising the respective precipitants and oils, for example, resulting in high mortality for seabirds, marine mammals and fish and disturbances in the ecological balance of the marine environment for many years. It is often problematic because it is considered to be toxic to many marine organisms. Furthermore, suspending the mixture of precipitant and oil in seawater allows for easier distribution over a large area by the current, so that adverse effects can still be observed in the distant areas.

Another method contemplates the use of microorganisms such as bacteria and algae that are effective for biodegradation of petroleum and petroleum products by inoculating contaminated media with each microorganism. For example, US Pat. No. 5,753,122 relates to an in situ thermally enhanced microbial recovery method for cleaning toxic components of petroleum fuel hydrogen and halogenated organic solvents. International Patent Application Publication No. WO 2010/080266 A2 relates to strains of Gordonia sihwensis that can be used to sequester and / or biodegrade hydrocarbons. International Patent Application Publication No. WO 2011/060107 A1 refers to an algae based biopurification system and method, in which algae grow in a photobioreactor with nutrients supplied from a nutrient system. European Patent Application Publication No. 0 962 492 A1 relates to compositions used for the biopurification of soils or fluids contaminated with microorganisms and organic compounds comprising chitin and / or derivatives thereof. International Patent Application Publication No. WO 2007/093993 A2 generally relates to the field of hydrocarbon decomposition, more specifically to environmentally safe bacterial compositions useful for cleaning and treating hydrocarbon contaminated water and surfaces. US Pat. No. 6,057,147 relates to an apparatus and method for improved biopurification of hydrocarbons removed from contaminated objects, comprising: (a) and (b): A container for cleaning, comprising: means for introducing a recycled biological purification solution (NATURES WAY PC ™) for cleaning the object, means for discharging the solution from the container into a biochamber reservoir and into the reservoir A container having means for screening particles from said solution upon introduction; And (b) means for adjusting the temperature from 90 ° F. to 112 ° F., means for venting the solution, means for stirring the solution, outlet means for a plurality of filters for filtering the solution, from the filter Said reservoir having means for inlet and means for removing filtered precipitates. International Patent Application Publication No. WO 2008/015688 A2 provides bioassistance for the treatment of hydrocarbon contaminated soils using new microorganisms that can decontaminate hydrocarbon contaminated soils with free flowing water, slurries or large amounts of gravel. Mention the method. US Patent Application Publication No. 2008/020947 A1 discloses a method for biopurifying microorganisms and oil contaminated soils with excellent biodegradability. International Patent Application Publication No. WO 2010/112696 A1 discloses also capable of degrading a large number of oil compound in solution in the aqueous effluent Lactococcus lattice Ravi N-Sys (Rhodococcus wratislaviensis) CNCM I-4088 or a bacterium Rhodococcus strive ribonucleic lance (Rhodococcus aetherivorans ) CNCM I-4089 bacteria. European Patent Application Publication 0594125 A2 refers to a carrier for supporting microorganisms, characterized in that it supports microorganisms for use in soil restoration and has pores and retains nutrients in or is nutrients for the microorganisms. European Patent No. 0962492 discloses the use of chitin and / or its derivatives as a biocatalyst or biostimulant for stimulating, accelerating, enhancing and protecting the growth of microorganisms, and adding chitin and / or its derivatives to the soil and fluids. It relates to a method for biopurifying soil and fluid contaminated with organic compounds, including.

However, the activity of the majority of bacteria capable of biodegrading hydrocarbon products is best when the temperature and concentration of inorganic nutrients are within certain optimum ranges. Thus, the obtained action of such bacteria under actual conditions, such as various temperatures and limited nutrients, is in some cases insufficient to achieve optimal biopurification of hydrocarbon contaminated media such as soil, seawater, groundwater and / or other contaminated media. .

Thus, alternative materials and methods for combining and biopurifying hydrocarbon-containing compositions provide better performance than existing materials and methods and effectively reduce the concentration of hydrocarbon-containing compositions in treated seawater, groundwater, soil and other media. I need it all the time.

This and other objects are solved by the protection subject of the present invention. According to a first aspect of the present invention there is provided a surface treated calcium carbonate for binding and biopurifying a hydrocarbon-containing composition having a decomposition rate for a hydrocarbon-containing composition that is at least 25% based on the total weight of the hydrocarbon-containing composition, At least 10% of the aliphatic carboxylic acid accessible surface area of calcium carbonate is coated by a coating comprising at least one aliphatic carboxylic acid having 5 to 24 carbon atoms and / or reaction products thereof.

The inventors have surprisingly obtained by the same method except that the material according to the present invention provides efficient binding and biopurification activity to the hydrocarbon containing composition, thereby not contacting the hydrocarbon contaminated medium with the surface treated calcium carbonate. It has been found that this results in a hydrocarbon contaminated medium containing an amount of hydrocarbon at least 25% lower than the amount of hydrocarbon in the corresponding hydrocarbon contaminated medium. More precisely, the inventors have found that the binding and biopurification activity for hydrocarbon-containing compositions can be improved by calcium carbonate surface-treated with defined aliphatic carboxylic acids.

It is to be understood that for the purposes of the present invention the following terms have the following meanings.

The term "calcium carbonate" in the sense of the present invention refers to heavy or natural calcium carbonate (GCC), and / or synthetic or hard calcium carbonate (PCC) and / or surface modified calcium carbonate (MCC). In the sense of the present invention "heavy calcium carbonate" (GCC) is obtained from natural sources such as limestone, marble, chalk or dolomite and milled by treatment, such as wet and / or dry processes such as cyclones or classifiers. Processed calcium carbonate through screening and / or fractionation. A "hard calcium carbonate" (PCC) in the sense of the present invention is generally a synthesized material obtained by precipitation after the reaction of lime with carbon dioxide in an aqueous environment, or by precipitation of calcium and carbonate ion sources in water. "Surface modified calcium carbonate" (MCC) in the sense of the present invention refers to natural calcium carbonate and / or hard calcium carbonate obtained by reacting calcium carbonate with acid and carbon dioxide prior to the preparation of the surface treated calcium carbonate, wherein Is formed in situ by acid treatment and / or supplied from an external source.

The term "surface treated" calcium carbonate in the sense of the present invention refers to heavy calcium carbonate and / or hard calcium carbonate and / or surface modifications that have been processed into aliphatic carboxylic acids through further processing steps such that the surface of the calcium carbonate particles has a higher hydrophobicity. Referred to as calcium carbonate.

The term "aliphatic carboxylic acid" in the sense of the present invention refers to a straight, branched, saturated, unsaturated or alicyclic organic compound composed of carbon and hydrogen. The organic compound further contains a carboxyl group located at the end of the carbon skeleton.

The term "aliphatic carboxylic acid accessible surface area" in the sense of the present invention is applied by coating techniques known to those skilled in the art, such as heat fluidized layer spray coating, heated wet coating, solvent assisted or self-assembled coating, etc. to aliphatic on the surface of the calcium carbonate particles. It refers to the surface of calcium carbonate particles accessible or exposed to aliphatic carboxylic acids forming a monolayer of carboxylic acid. In this regard, it should be recognized that the amount of aliphatic carboxylic acid required for the total saturation of the accessible surface area is defined as the monolayer concentration. Thus, higher concentrations may also be selected to form a bilayer or multilayer structure on the surface of the calcium carbonate particles. Such monolayer concentrations can be readily calculated by those skilled in the art based on the publications of Papirer, Schultz and Turchi, Eur.Polym. J., Vol. 20, No. 12, pp. 1155-1158, 1984. have.

The term “reaction product” in the sense of the present invention typically refers to a product obtained by contacting heavy calcium carbonate and / or light calcium carbonate with aliphatic carboxylic acids having 5 to 24 carbon atoms. The reaction product is preferably formed between the applied aliphatic carboxylic acid and a molecule located on the surface of heavy calcium carbonate and / or hard calcium carbonate.

The term "hydrocarbon containing composition" in the sense of the present invention refers to a composition comprising at least one type of hydrocarbon. As used herein, the term “hydrocarbon” refers to a straight, branched, saturated, unsaturated or cycloaliphatic organic compound composed of carbon and hydrogen. These organic compounds include alkanes, alkenes, alkynes and aromatic hydrocarbons.

The term "biocleaning" or "biocleaning" in the sense of the present invention refers to at least partial removal of contaminants by the use of microorganisms.

The term "decomposition rate" in the sense of the present invention refers to the amount of hydrocarbon in the hydrocarbon-containing composition within 60 days by the addition of the surface-treated calcium carbonate of the present invention as compared to the corresponding hydrocarbon-containing composition that does not contain surface-treated calcium carbonate. Corresponds to a decrease in.

Another aspect of the invention is directed to a method of combining and biopurifying a hydrocarbon containing composition comprising the following steps:

a) providing a hydrocarbon containing composition;

b) providing at least one surface treated calcium carbonate; And

c) contacting the hydrocarbon containing composition of step a) with the surface treated calcium carbonate of step b) to obtain a composite material comprising said surface treated calcium carbonate and said hydrocarbon containing composition.

The hydrocarbon containing composition is preferably crude oil and / or refined petroleum product selected from the group comprising gasoline, diesel fuel, aviation fuel, hydraulic oil, kerosene and mixtures thereof. In addition, step c) at least partially covers the surface of the hydrocarbon-containing composition of step a) with the surface treated calcium carbonate of step b), or / or the surface treatment of the hydrocarbon-containing composition of step a) It is preferably carried out by mixing with the prepared calcium carbonate. In addition, step c) has a weight ratio of the hydrocarbon-containing composition and the surface-treated calcium carbonate to 10: 1 to 1: 100, more preferably 1: 1 to 1:50, even more preferably 1: 1 to 1:25. Most preferably, 1: 1 to 1:15. Even further, the method further comprises the step of contacting the composite material obtained in step c) with a composition comprising at least one microorganism capable of decomposing at least one component of the hydrocarbon-containing composition. In addition, one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition are preferably selected from one or more strains of bacteria and / or fungi. One or more strains of bacteria are bakteo (Psychrobacter), Pseudomonas (Pseudomonas) in sayikeu shoe gambling Te Solarium (Pseudobacterium), evil cine Sat bakteo (Acinetobacter), Vibrio (Vibrio), Plano, Rhodococcus (Planococcus), evil Martino tumefaciens (Actinobacterium), ahsseuro bakteo (Arthrobacter), Marino bakteo (Marinobacter), tumefaciens (Methylobacterium) to when Taunus (Methylosinus), Pseudomonas (Methylomonas) methyl, methyl, Mycobacterium (Mycobacterium), no carboxylic Dia (Nocardia), Bacillus (Bacillus), Brevibacterium (Brevibacterium), micro Rhodococcus (Micrococcus), Corynebacterium (Corynebacterium), Sar or when (Sarcina), Streptomyces (Streptomyces), Flavobacterium (Flavobacterium ), Pseudomonas janto (Xanthomonas) and is selected from the group consisting of and mixtures thereof, more preferably bakteo article Racine coke (Psychrobacter glacincola) to sayikeu, Ill cine Sat bakteo It is selected from the group comprising coarse core Shetty (Acinetobacter calcoaceticus), evil cine Sat bakteo faecalis (Acinetobacter faecalis), and mixtures thereof are preferred. In addition, steps c) and d) are preferably carried out simultaneously or separately. It is also preferred that step c) and / or step d) is repeated one or more times.

A further aspect of the invention relates to the use of surface treated calcium carbonate for binding and biopurifying hydrocarbon containing compositions. Surface treated calcium carbonate is preferably used in soil, seawater, groundwater, flat water, shorelines, containers and / or reservoirs.

A further aspect of the invention relates to a composite material comprising a surface treated calcium carbonate and a hydrocarbon containing composition.

When preferred embodiments or technical details of the surface treated calcium carbonate of the present invention for bonding and biopurifying a hydrocarbon containing composition are mentioned below, these preferred embodiments or technical details combine and biopurify the hydrocarbon containing composition. It is to be understood that the invention also refers to a composite material comprising the invention, the use of the surface-treated calcium carbonate, and the surface-treated calcium carbonate and the hydrocarbon composition as defined herein, if applicable. . For example, when it is described that the surface treated calcium carbonate preferably comprises heavy calcium carbonate and / or hard calcium carbonate and / or surface modified calcium carbonate, the method of the invention, the use of the invention and The surface treated calcium carbonate provided in the composite material of the invention preferably comprises heavy calcium carbonate and / or hard calcium carbonate and / or surface modified calcium carbonate.

According to one preferred embodiment of the surface treated calcium carbonate of the present invention, the surface treated calcium carbonate comprises heavy calcium carbonate and / or hard calcium carbonate and / or surface modified calcium carbonate, preferably heavy calcium carbonate.

According to another preferred embodiment of the surface treated calcium carbonate of the present invention, the source of heavy calcium carbonate (GCC) is selected from marble, chalk, calcite, dolomite, limestone and mixtures thereof, and / or hard calcium carbonate (PCC) ) Is selected from one or more of the mineralogy crystalline forms of aragonite, batterite and calcite.

According to another preferred embodiment of the surface treated calcium carbonate of the present invention, the surface treated calcium carbonate is 0.1 μm to 250 μm, preferably 1 μm to 200 μm, more preferably 1 μm to 150 μm, even more Preferably it has a weight median particle diameter d ₅₀ value between 1 μm and 100 μm, most preferably between 3 μm and 100 μm.

According to one preferred embodiment of the surface-treated calcium carbonate of the present invention, the coating of the surface-treated calcium carbonate is made of pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tri Decanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosyl acid, behenic acid, tricosic acid, lignoceric acid and mixtures thereof At least one aliphatic carboxylic acid selected from the group consisting of, preferably the aliphatic carboxylic acid comprises octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and mixtures thereof And most preferably the aliphatic carboxylic acid is selected from the group consisting of myristic acid, palmitic acid, stearic acid and mixtures thereof.

According to another preferred embodiment of the surface treated calcium carbonate of the present invention, at least 20% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate, preferably at least 30% of the accessible surface area, most preferably the accessible At least 50% of the surface area is covered by a coating comprising at least one aliphatic carboxylic acid and / or its reaction product.

According to another preferred embodiment of the surface treated calcium carbonate of the present invention, the surface treated calcium carbonate further comprises one or more microorganisms capable of degrading one or more components of the hydrocarbon containing composition.

According to one preferred embodiment of the surface treated calcium carbonate of the present invention, the surface treated calcium carbonate is immobilized with one or more microorganisms capable of degrading one or more components of the hydrocarbon containing composition.

According to another preferred embodiment of the surface treated calcium carbonate of the present invention, one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition are selected from one or more strains of bacteria and / or fungi.

According to another preferred embodiment of the surface treated calcium carbonate of the present invention, one or more strains of bacteria and / or fungi are one or more strains of petroleum degraded bacteria and / or petroleum degraded fungi.

According to one preferred embodiment of the surface treated calcium carbonate of the present invention, one or more strains of bacteria are cyclobacter, Pseudomonas, Pseudobacterium, Axinetobacter, Vibrio, Planococcus, Actinobacterium, Atherosclerosis. Bacter, Marinobacter, Methylosinus, Methylonomonas, Methylobacterium, Mycobacterium, Nocardia, Bacillus, Brevibacterium, Microcacus, Corynebacterium, Sarcina, Streptomyces, Flavobacterium, xanthomonas, and mixtures thereof, more preferably cyclobacter glacincola, axinetobacter calcoaceticus, axinebacter faecalis and mixtures thereof It is selected from the group containing.

According to another preferred embodiment of the surface treated calcium carbonate of the present invention, the surface treated calcium carbonate is in powder form and / or in granule form or slurry form.

According to another preferred embodiment of the surface treated calcium carbonate of the present invention, the surface treated calcium carbonate is incorporated into the nonwoven. The surface treated calcium carbonate is preferably incorporated into the biodegradable nonwoven.

In the following further preferred embodiments of the invention are mentioned.

According to the surface treated calcium carbonate of the present invention, at least 10% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate is by a coating comprising at least one aliphatic carboxylic acid having 5 to 24 carbon atoms and / or reaction products thereof. Is covered.

In one preferred embodiment, the surface treated calcium carbonate comprises heavy (or natural) calcium carbonate (GCC) or hard (or synthetic) calcium carbonate (PCC) or surface modified calcium carbonate (MCC). In another preferred embodiment, the surface treated calcium carbonate comprises a mixture of two or more calcium carbonates selected from GCC, PCC and MCC. For example, the surface treated calcium carbonate includes a mixture of GCC and PCC. Alternatively, the surface treated calcium carbonate comprises a mixture of GCC and MCC. Alternatively, the surface treated calcium carbonate comprises a mixture of PCC and MCC.

In one particularly preferred embodiment, the surface treated calcium carbonate comprises heavy calcium carbonate.

Heavy (or natural) calcium carbonate (GCC) is understood to be a naturally occurring form of calcium carbonate mined from sedimentary rocks, such as limestone or chalk, or metamorphic surrogate. Calcium carbonate is known to exist as three types of crystalline polymorphs: calcite, aragonite and batterite. Calcite, the most common crystalline polymorph, is considered to be the most stable crystalline form of calcium carbonate. Aragonite with scattered or agglomerated needle tetragonal structures is less common. Batterite is the rarest calcium carbonate polymorph and is generally unstable. Heavy calcium carbonate is almost entirely calcite polymorph, which is described as triangular rhombohedron and represents the most stable form of calcium carbonate polymorph.

Preferably, the source of heavy calcium carbonate is selected from the group comprising marble, chalk, calcite, dolomite, limestone and mixtures thereof. In a preferred embodiment, the source of heavy calcium carbonate is calcite.

The term "source" of calcium carbonate in the sense of the present invention refers to a naturally occurring mineral from which calcium carbonate is obtained. The source of calcium carbonate may further comprise naturally occurring components such as magnesium carbonate, aluminosilicates and the like.

Additionally or alternatively, the surface treated calcium carbonate includes hard calcium carbonate (PCC). Calcium carbonate polymorphs of the PPC type often include, in addition to calcite, aragonite types with acicular tetragonal form and less stable polymorphs of hexagonal batterite type with much lower stability than aragonite. Different PCC forms can be identified according to their characteristic x-ray powder diffraction (XRD) peaks. PCC synthesis most commonly comprises the step of contacting carbon dioxide with a calcium hydroxide solution (most frequently provided in the formation of an aqueous suspension of calcium oxide, also known as quicklime and a suspension of calcium oxide, commonly known as lime oil). Caused by the reaction. Depending on the reaction conditions, this PCC can come in various forms, including both stable and unstable polymorphs depending on the reaction conditions. Indeed, PCC often represents a thermodynamically unstable calcium carbonate material. As mentioned in the context of the present invention, PCC means a synthetic calcium carbonate product obtained by carbonation of a slurry of calcium hydroxide, commonly referred to in the art as lime slurry or lime oil, especially when derived from finely divided calcium oxide particles in water. Will be understood.

Preferred hard calcium carbonates are selected from mineralogy crystalline forms of aragonite, batterite or calcite and mixtures thereof.

Additionally or alternatively, the GCC or PCC may comprise GCC and / or PCC; And a surface reacted to form a surface modified calcium carbonate that is a material comprising a calcium noncarbonate salt having an insoluble and at least partially crystalline extending from the surface of at least a portion of the calcium carbonate. Such surface modified products are described, for example, in International Patent Application Publication No. WO 00/39222, International Patent Application Publication No. WO 2004/083316, International Patent Application Publication No. WO 2005/121257, International Patent Application Publication No. WO 2009 / 074492, European Patent Application Publication No. 2 264 108 A1 and European Patent Application Publication No. 2 264 109 A1.

For example, surface modified calcium carbonate is obtained by reacting natural calcium carbonate and / or hard calcium carbonate with acid or carbon dioxide prior to the preparation of the surface treated calcium carbonate, where carbon dioxide is formed in situ by the acid treatment and And / or from an external source. The acid treatment can be carried out by using an acid having _a pK _a of 2.5 or less at 25 ° C. When pK _a at 25 ° C. is 0 or less, the acid is preferably selected from sulfuric acid, hydrochloric acid and mixtures thereof. If the pK _a at 25 ℃ of from 0 to 2.5, the acid is preferably ^{_{H 2 SO 3, M + HSO}} 4 - (M + is being an alkali metal ion selected from the group comprising sodium and potassium), H ₃ PO ₄ , Oxalic acid and mixtures thereof.

In a particularly preferred embodiment, the calcium carbonate particles of the surface treated calcium carbonate of the present invention are 0.1 μm to 250 μm, preferably 1 μm to 200 μm, more preferably 1 μm to 1 as measured according to the sedimentation method before the surface treatment. Weight median particle diameter d _{50 of} 150 μm, most preferably 1 μm to 100 μm Lt; / RTI > In one particularly preferred embodiment, the calcium carbonate particles of the surface treated calcium carbonate of the present invention have a weight median particle diameter d ₅₀ value of 3 μm to 100 μm before the surface treatment. For example, the calcium carbonate particles of the surface treated calcium carbonate have a weight median particle diameter d ₅₀ value of 19.5 μm before the surface treatment. Alternatively, the calcium carbonate particles of the surface treated calcium carbonate have a weight median particle diameter d ₅₀ value of 1.4 μm before the surface treatment. Calcium carbonate particles having a d ₉₈ of less than 100 μm, preferably less than 85 μm, for example 83 μm, may also be advantageous. Alternatively, calcium carbonate particles having a d ₉₈ of less than 20 μm, preferably less than 10 μm, for example 5 μm, may be advantageous.

As used herein and as defined generally in the art, the weight median particle diameter “d ₉₈ ” value is the size when a particle having a diameter equal to the specified value occupies 98% (average point) of the particle volume or mass. Is defined. Gravity median particle diameter was measured according to the sedimentation method. The sedimentation method is an analysis of sedimentation behavior in the gravitational field. Measurements are made using the Sedigraph ™ 5100 from Micromeritics Instrument Corporation.

The calcium carbonate particles of the surface treated calcium carbonate of the present invention are preferably 0.5 m 2 / g to 120 m 2 / g, preferably 0.5 m 2 / g to 100 m 2 / g measured by using nitrogen and a BET method before surface treatment. , More preferably from 0.5 m 2 / g to 75 m 2 / g, most preferably from 0.5 m 2 / g to 50 m 2 / g. For example, the calcium carbonate particles of the surface treated calcium carbonate have a specific surface area of 0.5 m 2 / g to 10 m 2 / g before the surface treatment. Alternatively, the calcium carbonate particles of the surface treated calcium carbonate of the present invention have a specific surface area of 5 m 2 / g to 15 m 2 / g.

In one preferred embodiment, the calcium carbonate particles of the surface treated calcium carbonate of the present invention have a specific surface area in the range of 0.5 m 2 / g to 120 m 2 / g and a weight median particle diameter in the range of 0.1 μm to 250 μm before surface treatment. _{Has a} value of ₅₀ . More preferably, the specific surface area before the surface treatment is in the range of 0.5 m 2 / g to 100 m 2 / g and the weight median particle diameter d ₅₀ value is in the range of 1 μm to 200 μm. Even more preferably, the specific surface area before the surface treatment is in the range of 0.5 m 2 / g to 75 m 2 / g and the weight median particle diameter is in the range of 1 μm to 150 μm. Most preferably, the specific surface area before the surface treatment is in the range of 0.5 m 2 / g to 50 m 2 / g and the weight median particle diameter d ₅₀ value is in the range of 1 μm to 100 μm. For example, the calcium carbonate particles of the surface treated calcium carbonate of the present invention have a specific surface area in the range of 5 m 2 / g to 15 m 2 / g and a weight median particle diameter d ₅₀ value of 1.4 μm. Alternatively, the calcium carbonate particles of the surface treated calcium carbonate of the present invention have a specific surface area in the range of 0.5 m 2 / g to 10 m 2 / g and a weight median particle diameter d ₅₀ value of 19.5 μm.

According to the surface treated calcium carbonate of the present invention, at least 10% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate is coated by a coating comprising at least one aliphatic carboxylic acid having 5 to 24 carbon atoms and / or reaction products thereof. It is.

In this regard, one or more aliphatic carboxylic acids may be selected from one or more straight, branched, saturated, unsaturated and / or alicyclic carboxylic acids. Preferably, the aliphatic carboxylic acid is a monocarboxylic acid. That is, aliphatic carboxylic acids are characterized by the presence of a single carboxyl group. The carboxyl group is located at the end of the carbon skeleton.

In one preferred embodiment, the at least one aliphatic carboxylic acid is selected from saturated unbranched carboxylic acids. That is, the at least one aliphatic carboxylic acid is pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecane Acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosyl acid, behenic acid, tricosyl acid, lignoseric acid and mixtures thereof.

In a further preferred embodiment, the at least one aliphatic carboxylic acid is selected from the group consisting of octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and mixtures thereof. Preferably, the at least one aliphatic carboxylic acid is selected from the group consisting of myristic acid, palmitic acid, stearic acid and mixtures thereof.

In a particularly preferred embodiment, the aliphatic carboxylic acid is stearic acid.

In one preferred embodiment, the aliphatic carboxylic acid comprises a mixture of two or more aliphatic carboxylic acids having 5 to 24 carbon atoms. Preferably, when the aliphatic carboxylic acid comprises a mixture of two or more aliphatic carboxylic acids having from 5 to 24 carbon atoms, one aliphatic carboxylic acid is stearic acid.

In a further preferred embodiment, the aliphatic carboxylic acid comprises a mixture of two aliphatic carboxylic acids having from 5 to 24 carbon atoms, wherein one aliphatic carboxylic acid is stearic acid and the other is octanoic acid, myristic acid, palmitic Acid, arachidic acid, behenic acid, and lignoseric acid.

When the aliphatic carboxylic acid comprises a mixture of two aliphatic carboxylic acids having 5 to 24 carbon atoms, the molar ratio of stearic acid and the second aliphatic carboxylic acid is 99: 1 to 1:99, more preferably 50: 1 to 1 : 50, even more preferably 25: 1 to 1:25, most preferably 10: 1 to 1:10. In one particularly preferred embodiment of the invention, the molar ratio of stearic acid and second aliphatic carboxylic acid is from 90: 1 to 1: 1, more preferably from 90: 1 to 10: 1, most preferably from 90: 1 to 50: 1 In another preferred embodiment, the molar ratio of stearic acid and second aliphatic carboxylic acid is 1: 1.

If the aliphatic carboxylic acid comprises a mixture of two aliphatic carboxylic acids having from 5 to 24 carbon atoms, at least 10% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate is preferably stearic acid, myristic acid and / or their It is covered by a coating comprising a mixture of reaction products. In a further preferred embodiment, at least 10% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate is coated with a coating comprising a mixture of stearic acid, palmitic acid and / or reaction products thereof. In another preferred embodiment, at least 10% of the aliphatic carboxylic acid accessible surface area of calcium carbonate is covered by a coating comprising stearic acid, arachidic acid and / or a mixture of reaction products thereof. In another preferred embodiment, at least 10% of the aliphatic carboxylic acid accessible surface area of calcium carbonate is coated with a coating comprising stearic acid, behenic acid and / or a mixture of reaction products thereof. In a further preferred embodiment, at least 10% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate is covered by a coating comprising a mixture of stearic acid, lignoseric acid and / or reaction products thereof. In another preferred embodiment, at least 10% of the aliphatic carboxylic acid accessible surface area of calcium carbonate is coated with a coating comprising stearic acid, octanoic acid and / or a mixture of reaction products thereof.

The at least one aliphatic carboxylic acid is such that the total weight of the reaction product of the at least one aliphatic carboxylic acid and / or the at least one aliphatic carboxylic acid on the surface of the surface treated calcium carbonate product is from 0.01% to 50% by weight of calcium carbonate. It is preferred to be present in the coating which coats the calcium carbonate in an amount such that it is.

In one preferred embodiment, the at least one aliphatic carboxylic acid has a total weight of the reaction product of said at least one aliphatic carboxylic acid and / or said at least one aliphatic carboxylic acid on the surface of the surface treated calcium carbonate product, More preferably less than 15% w / w, most preferably less than 10% w / w in the coating coating the calcium carbonate.

In another preferred embodiment, the reaction product of at least one aliphatic carboxylic acid and / or said at least one aliphatic carboxylic acid is from about 0.1% to 10% by weight, more preferably from about 0.1% to 8% by weight based on the dry weight of calcium carbonate Present in a coating covering at least 10% of the aliphatic carboxylic acid accessible surface area of calcium carbonate in an amount of from about 0.2% to 5% by weight, most preferably from about 0.2% to 2.5% by weight. do.

Alternatively, at least 20% of the aliphatic carboxylic acid accessible surface area of calcium carbonate is coated by a coating comprising at least one aliphatic carboxylic acid and / or reaction product of said at least one aliphatic carboxylic acid. In a preferred embodiment, at least 30% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate particles, preferably at least 50% of the aliphatic carboxylic acid accessible surface area comprises the reaction product of at least one aliphatic carboxylic acid and / or said at least one aliphatic carboxylic acid. Coated by coating. In another preferred embodiment, at least 75% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate particles is covered by a coating comprising at least one aliphatic carboxylic acid and / or a reaction product of said at least one aliphatic carboxylic acid. For example, at least 90% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate particles is covered by a coating comprising at least one aliphatic carboxylic acid and / or reaction product of said at least one aliphatic carboxylic acid. Alternatively, calcium carbonate particles Aliphatic carboxylic acids of from 10% to 25% of the accessible surface area are covered by a coating comprising at least one aliphatic carboxylic acid and / or reaction product of said at least one aliphatic carboxylic acid.

In one preferred embodiment, at least 75% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate particles is coated by a coating comprising the reaction product of stearic acid and / or stearic acid.

In another preferred embodiment, 10% to 25% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate particles is coated by a coating comprising the reaction product of stearic acid and / or stearic acid.

In one preferred embodiment, the at least one aliphatic carboxylic acid is at most 5 g per 100 ml of water, preferably at most 2.5 g per 100 ml of water, even more preferably at most 1 g per 100 ml of water, most preferably water Up to 0.5 g of solubility per 100 ml. In one particularly preferred embodiment, the at least one aliphatic carboxylic acid is immiscible in water.

The surface treated calcium carbonate is preferably present in the form of particulate material and may have a particle size distribution as is commonly used for the material (s) involved in the treatment of hydrocarbon contaminated media. In general, the weight median particle diameter d ₅₀ value of the surface treated calcium carbonate is from 0.1 μm to 250 μm, preferably from 1 μm to 200 μm, more preferably from 1 μm to 150 μm, even more as measured according to the sedimentation method. It is preferably in the range of 1 μm to 100 μm, most preferably 3 μm to 100 μm. For example, the surface treated calcium carbonate has a weight median particle diameter d ₅₀ value of 19.5 μm. Alternatively, the surface treated calcium carbonate has a weight median particle diameter d ₅₀ value of 1.4 μm. Surface treated calcium carbonates having a d ₉₈ of less than 100 μm, preferably less than 85 μm, for example 83 μm, may also be advantageous. Alternatively, surface treated calcium carbonate having a d ₉₈ of less than 20 μm, preferably less than 10 μm, for example 5 μm, may be advantageous.

The surface treated calcium carbonate of the present invention is preferably 0.5 m 2 / g to 120 m 2 / g, preferably 0.5 m 2 / g to 100 m 2 / g, more preferably 0.5 m 2, measured by using nitrogen and the BET method. It has a specific surface area of / g to 75 m 2 / g. For example, the surface treated calcium carbonate has a specific surface area of 0.5 m 2 / g to 10 m 2 / g, for example, 0.61 m 2 / g. Alternatively, the surface treated calcium carbonate has a specific surface area of 5 m 2 / g to 15 m 2 / g, for example 5.5 m 2 / g.

In one preferred embodiment, the surface treated calcium carbonate further comprises one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition.

For the purposes of the present invention, microorganisms that “decompose” one or more components of a hydrocarbon-containing composition may use one or more components of the hydrocarbon-containing composition in an inert form and / or in smaller amounts, for example, by using these substrates as intermediates in their route. Corresponds to a microorganism with the ability to convert to a molecule.

If the surface treated calcium carbonate further comprises one or more microorganisms capable of decomposing one or more components of the hydrocarbon-containing composition, the surface treated calcium carbonate and the one or more microorganisms may be present in separate forms and / or Surface treated calcium carbonate is immobilized with the one or more microorganisms.

If the surface-treated calcium carbonate and one or more microorganisms capable of decomposing one or more components of the hydrocarbon-containing composition are in separate forms, both the surface-treated calcium carbonate and the one or more microorganisms are preferably in the form of suspensions. Exists as. Such suspensions may be present according to well known forms and may be prepared by methods well known to those skilled in the art.

For example, the surface treated calcium carbonate of the present invention is in powder form and / or granule form, and one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition are in the form of an aqueous suspension. Alternatively, the surface treated calcium carbonate of the present invention is in the form of a slurry and one or more microorganisms capable of decomposing one or more components of the hydrocarbon-containing composition are in the form of an aqueous suspension. Optionally, the aqueous suspension of one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition further comprises nutrients such as phosphates, ammonium nitrate, proteins, alkali metal ammonium phosphates, glucose, dextrose, urea, yeast, and the like. Include. Additionally or alternatively, these nutrients may be present in the slurry of the surface treated calcium carbonate.

In one particularly preferred embodiment, the surface treated calcium carbonate is immobilized with one or more microorganisms that can degrade one or more components of the hydrocarbon-containing composition.

In general, the surface treated calcium carbonate is immobilized with one or more microorganisms according to well known methods. For example, an immobilization method may be employed that includes exposing the surface treated calcium carbonate to an aqueous suspension of one or more microorganisms to be immobilized. If desired, such exposure may be exposure only for a time sufficient to allow the microorganism to adsorb on the surface treated calcium carbonate. Alternatively, if the aqueous suspension comprises a nutrient broth, this exposure may be a longer time exposure that will allow some growth of the microorganisms during the immobilization procedure for the surface treated calcium carbonate. Additionally or alternatively, the immobilization method may comprise confining the microorganisms to the pores of the surface treated calcium carbonate under reduced pressure.

In this regard, there are no particular limitations on the microorganisms used with the surface treated calcium carbonate of the present invention, but suitable microorganisms have the ability to degrade to the various hydrocarbons commonly found in crude oil and / or refined petroleum products. Selected from known microorganisms. Examples of microorganisms capable of degrading one or more components of a hydrocarbon-containing composition that may suitably be used in the present invention are selected from the group comprising one or more strains of bacteria and / or fungi.

In one preferred embodiment, one or more strains of bacteria and / or fungi capable of degrading one or more components of the hydrocarbon-containing composition are one or more strains of petroleum degraded bacteria and / or petroleum degraded fungi.

In one preferred embodiment, one or more strains of bacteria and / or fungi capable of degrading one or more components of the hydrocarbon-containing composition are petroleum degrading bacteria or one or more strains of petroleum degrading fungi. Alternatively, one or more strains of bacteria and / or fungi that can degrade one or more components of the hydrocarbon-containing composition are one or more strains of petroleum degraded bacteria and petroleum degraded fungi.

Specific examples of bacterial strains that may be suitably used in the present invention include Cyclobacter, Pseudomonas, Pseudobacterium, Acinetobacter, Vibrio, Planococcus, Actinobacterium, Aslobacter, Marinobacter, Methylose Nose, methyllomonas, methyllobacterium, mycobacterium, nocardia, bacillus, brevibacterium, micrococcus, corynebacterium, sarcina, streptomyces, flabobacterium, xanthomonas and Selected from the group comprising mixtures thereof.

In one particularly preferred embodiment, the one or more strains of bacteria are selected from the group comprising Cyclobacter glacincola, Axinetobacter calcoaceticus, Axinetobacter faecalis and mixtures thereof.

In one preferred embodiment, one or more strains of bacteria capable of digesting one or more components of the hydrocarbon-containing composition are one or more genetically modified bacterial strains. That is, the bacteria have been genetically engineered to upregulate metabolic pathways to degrade one or more components of the hydrocarbon-containing composition.

In one preferred embodiment, the one or more fungal strains capable of degrading one or more components of the hydrocarbon containing composition are one or more filamentous fungal strains.

Specific examples of the fungal strain that can be suitably used in the present invention include asbestos peogil Russ Plastic bus (Aspergillus flavus), Asda peogil Russ Fu Micah test (Aspergillus fumigates), you AAS peogil Russ Gershon (Aspergillus niger), Asda peogil Russ nibe mouse (Aspergillus niveus ), Aspergillus terreus ), Aspergillus versicolor), Fusarium (Fusarium) species Mortierella (Mortierella) species, Mu cor (Mucor), Mai Celia (Mycelia), Penny room Solarium nose reel pilrum (Penicillium corylophilum), L indeed My process nibe mouse (Paecilomyces niveus ), Paecilomyces variotti , Rhizopus , Talamoryces , Trichoderma species, and mixtures thereof.

In one preferred embodiment, one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition comprise at least two components of the hydrocarbon-containing composition, preferably at least three components of the hydrocarbon-containing composition, most preferably a hydrocarbon-containing composition. A microorganism capable of decomposing a plurality of components.

One or more microorganisms capable of decomposing one or more components of the hydrocarbon-containing composition are those wherein the one or more microorganisms are at least 25%, preferably at least 40%, more preferably at least 40% of the hydrocarbon-containing composition based on the total weight of the hydrocarbon-containing composition. At least 50%, even more preferably at least 60%, most preferably at least 70%. In one particularly preferred embodiment, the one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition exhibit a degradation rate of at least 75% for the hydrocarbon-containing composition based on the total weight of the hydrocarbon-containing composition.

In one preferred embodiment, the one or more microorganisms that can degrade one or more components of the hydrocarbon-containing composition are a mixture of two or more microorganisms that can degrade one or more components of the hydrocarbon-containing composition. Preferably, the one or more microorganisms that can degrade one or more components of the hydrocarbon-containing composition is a mixture of three or more microorganisms that can degrade one or more components of the hydrocarbon-containing composition. Preferably, when the one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition are a mixture of two or more microorganisms, one microorganism is a bacterial strain of Cyclobacter glacincola.

The surface treated calcium carbonate of the present invention may be in any suitable form, for example in the form of granules or powders or in the form of a cake. Preferably, the surface treated calcium carbonate is present in powder form and / or granule form. In a preferred embodiment, the surface treated calcium carbonate is in powder form. Alternatively, the surface treated calcium carbonate can be present as an aqueous suspension, for example in the form of a slurry.

"Slurry" or "suspension" in the sense of the present invention includes an insoluble solid, ie surface treated calcium carbonate and water, and optionally additional additives. Suspensions typically contain large amounts of solids and have a higher viscosity and generally higher density than the liquids that formed them. It is recognized in the art that the general term "dispersion" covers in particular "suspension" or "slurry" as a particular type of dispersion.

In one preferred embodiment, the surface treated calcium carbonate of the present invention is characterized in that the slurry is from 1% to 80% by weight, more preferably from 3% to 60% by weight, even more preferably 5% by weight of the slurry. It has a content of the surface-treated calcium carbonate in the range of 40% by weight.

The surface treated calcium carbonate can optionally be maintained in a suspension more stabilized by a dispersant. Conventional dispersants known to those skilled in the art can be used. A preferred dispersant is polyacrylic acid.

Within the context of the present invention, it is also possible to provide a nonwoven comprising the surface treated calcium carbonate of the present invention. In this regard, conventional nonwovens known to those skilled in the art can be used. For example, a nonwoven fabric produced by forming a fiber layer (fiber web) by a dry method, a wet process, or the like and bonding the fibers in the fiber layer with each other by a chemical bonding method, a thermal bonding method, or the like may be used.

In one preferred embodiment, the surface treated calcium carbonate of the present invention is incorporated into a biodegradable nonwoven. If the nonwoven is biodegradable, the nonwoven is preferably cotton, flax, hemp, jute, ramie, coir, sisal, abaca, sheep, bagasse or It is made of a mixture of these. For example, biodegradable nonwovens are made of cotton and / or flax. The biodegradable nonwovens are preferably made of cotton or flax.

In one preferred embodiment, the nonwoven comprises the surface treated calcium carbonate of the present invention immobilized with one or more microorganisms capable of breaking down one or more components of the hydrocarbon-containing composition. Optionally, the nonwoven may further comprise nutrients as described above.

In another preferred embodiment, the nonwoven comprises an aqueous suspension of the surface treated calcium carbonate of the present invention, and one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition, and optionally the aqueous The suspension further comprises nutrients as described above.

According to the present invention, the surface treated calcium carbonate is suitable for effectively binding and biopurifying the hydrocarbon containing composition and has a decomposition rate for the hydrocarbon containing composition which is 25% or more based on the total weight of the hydrocarbon containing composition.

In one preferred embodiment, the surface treated calcium carbonate is at least 40%, preferably at least 50%, more preferably at least 60%, most preferably 70 based on the total weight of the hydrocarbon-containing composition. It is chosen such that a decomposition rate of at least% is obtained. In one particularly preferred embodiment, the surface treated calcium carbonate is selected such that at least 75% degradation rate for the hydrocarbon containing composition is obtained based on the total weight of the hydrocarbon containing composition.

As used herein, “hydrocarbon containing composition” refers to a composition comprising one or more hydrocarbons. That is, the composition comprises one or more types of hydrocarbons. In one preferred embodiment, the hydrocarbon containing composition comprises two or more hydrocarbons. That is, the composition comprises two or more types of hydrocarbons. In a particularly preferred embodiment, the hydrocarbon containing composition comprises a plurality of hydrocarbons. That is, the composition is a mixture of hydrocarbons of different types.

Examples of hydrocarbons include aliphatic hydrocarbons, aromatic hydrocarbons, nitro-aromatic hydrocarbons, halo-aliphatic hydrocarbons, halo-aromatic hydrocarbons, and mixtures thereof. In one preferred embodiment, the hydrocarbon containing composition comprises alkanes such as methane, ethane, propane, butane, isobutane, pentane, isopentane, neopentane, hexane, heptane, 2,4-dimethylheptane, octane, isooctane, nonane, Decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane and eicosane, and mixtures thereof; Alkenes such as ethene, propene, butene, butadiene, isobutene, pentene, hexene, heptene, octene, nonene and decene, and mixtures thereof; Alkynes such as ethyne, propyne, butyne, fentin, hexin, heptin, octin, nonnin and desine, and mixtures thereof; Cycloalkanes such as cyclopropane, cyclobutane, methylcyclopropane, cyclopentane, methylcyclopentane, cyclohexane, cycloheptane, methylcyclohexane, cyclooctane, cyclononane and cyclodecane, and mixtures thereof; Alkadienes such as allene, butadiene, pentadiene, isoprene, hexadiene, heptadiene, octadiene, nonadiene, decadiene and mixtures thereof; And aromatic hydrocarbons such as benzene, naphthalene, anthracene, acenaphthene, acenaphthylene, benzopyrene, pyrene, toluene, xylene, trimethylbenzene, ethylbenzene, methylnaphthalene, aniline, phenol, phenanthrene and dimethylphenol, and their At least one type of hydrocarbon selected from the group comprising the mixture.

The exact chemical composition of crude oil and refined petroleum products depends on the origin of the crude oil.

In one preferred embodiment, the hydrocarbon-containing composition comprises 10% to 90% by weight, preferably 15% to 75% by weight, more preferably 20% to 65% by weight, based on the total weight of the hydrocarbon-containing composition. Even more preferably from 25% to 65% by weight, most preferably from 30% to 65% by weight of one type of hydrocarbon.

In a further preferred embodiment, the hydrocarbon containing composition comprises two or more types of hydrocarbons, wherein each hydrocarbon is present in a constant amount. In one particularly preferred embodiment, the first type of hydrocarbon is present in an amount of 1% to 25% by weight based on the total weight of the hydrocarbon containing composition and the second type of hydrocarbon is based on the total weight of the hydrocarbon containing composition It is present in an amount from 70% to 90% by weight. In another preferred embodiment, the first type of hydrocarbon is present in an amount of 10% to 50% by weight, based on the total weight of the hydrocarbon-containing composition, and the second type of hydrocarbon is based on the total weight of the hydrocarbon-containing composition. It is present in an amount of 40% by weight to 80% by weight. In a further preferred embodiment, the first type of hydrocarbon is present in an amount of 20% to 60% by weight based on the total weight of the hydrocarbon containing composition and the second type of hydrocarbon is 30 based on the total weight of the hydrocarbon containing composition. It is present in an amount of from 75% by weight.

In one particularly preferred embodiment, the mixture of four to six types of hydrocarbons is at least 40% by weight, more preferably at least 50% by weight and most preferably at least 60% by weight based on the total weight of the hydrocarbon-containing composition. Exists as. For example, a mixture of five types of hydrocarbons is present in an amount of at least 40% by weight, more preferably at least 50% by weight and most preferably at least 60% by weight, based on the total weight of the hydrocarbon-containing composition.

In one preferred embodiment, the hydrocarbon containing composition is crude oil and / or refined petroleum product selected from the group comprising gasoline, diesel fuel, aviation fuel, hydraulic oil, kerosene and mixtures thereof.

According to another aspect of the invention, a method of binding and biopurifying a hydrocarbon containing composition comprises providing a hydrocarbon containing composition. Another step of the process involves the provision of one or more surface treated calcium carbonates of the invention, wherein at least 10% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate has at least one aliphatic having from 5 to 24 carbon atoms Coated by a coating comprising a carboxylic acid and / or a reaction product thereof. Further steps of the method of the present invention include contacting the hydrocarbon containing composition with at least one surface treated calcium carbonate to obtain a composite material comprising the surface treated calcium carbonate and the hydrocarbon containing composition.

In one preferred embodiment, the hydrocarbon containing composition is crude oil and / or refined petroleum product selected from the group comprising gasoline, diesel fuel, aviation fuel, hydraulic oil, kerosene and mixtures thereof.

In another preferred embodiment, contacting the hydrocarbon containing composition with at least one surface treated calcium carbonate is preferably carried out such that the surface of the hydrocarbon containing composition is at least partially covered with at least one surface treated calcium carbonate, wherein At least 10% of the aliphatic carboxylic acid accessible surface area of the calcium carbonate is coated by a coating comprising at least one aliphatic carboxylic acid having from 5 to 24 carbon atoms and a reaction product thereof. Additionally or alternatively, contacting the hydrocarbon containing composition with at least one surface treated calcium carbonate is preferably carried out such that the hydrocarbon containing composition of step a) is mixed with the surface treated calcium carbonate of step b). Those skilled in the art will adopt mixing conditions (eg, configuration of the mixing rate) depending on their needs and available apparatus.

In one particularly preferred embodiment, the surface treated calcium carbonate is incorporated into a nonwoven that can be disposed on the surface of the hydrocarbon containing composition. In one preferred embodiment, the nonwoven is a biodegradable nonwoven.

In a further preferred embodiment, the surface treated calcium carbonate is immobilized with one or more microorganisms that can degrade one or more components of the hydrocarbon-containing composition.

The treatment time for carrying out contact of the at least one hydrocarbon containing composition with the at least one surface treated calcium carbonate is at least 5 minutes, preferably at least 1 hour, more preferably at least 12 hours, most preferably at least 24 hours. It is carried out for the above time. In general, the contact time of the hydrocarbon containing composition with one or more surface treated calcium carbonates is determined by the extent of hydrocarbon contamination and the medium being treated. For example, when the degree of hydrocarbon contamination is limited to a spatially confined area, for example when hydraulic oil leaks on the sealed concrete, the treatment time is as short as, for example, 5 minutes to 6 hours. If the degree of hydrocarbon contamination is very large, for example, for hydrocarbon contamination of seawater and corresponding shorelines affected by oil spills, the treatment time can be as long as about 12 hours to 90 days, for example. In one preferred embodiment, the treatment time is about 60 days to 90 days.

The amount of surface treated calcium carbonate according to the invention is high enough to provide sufficient binding in the hydrocarbon containing composition, ie to provide efficient binding and biopurification activity for one or more types of hydrocarbons present in the hydrocarbon containing composition, but at the same time a significant amount of unbonding. Surface treated calcium carbonate is selected so low that it is not observed on the contaminated medium being treated. In other words, by utilizing the surface treated calcium carbonate or the process of the present invention, efficient binding and biopurification activity is provided and a large (and therefore unwanted) amount of surface treated calcium carbonate is avoided.

In one preferred embodiment, the contact of the at least one hydrocarbon containing composition with the at least one surface treated calcium carbonate has a weight ratio of the hydrocarbon containing composition and the surface treated calcium carbonate from 10: 1 to 1: 100, more preferably from 1: 1 to 1:50, even more preferably 1: 1 to 1:25, most preferably 1: 1 to 1:15.

In one preferred embodiment, the method further comprises contacting the composite material obtained in step c) with a composition comprising at least one microorganism capable of degrading at least one component of the hydrocarbon-containing composition.

If a composite material comprising a surface treated calcium carbonate and a hydrocarbon containing composition is further contacted with a composition comprising one or more microorganisms capable of degrading one or more components of the hydrocarbon containing composition, the composition is any known to those skilled in the art. It may be provided in an appropriate form.

For example, a composition comprising one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition of step d) may be provided in the form of an aqueous suspension. If the one or more microorganisms are one or more strains of bacteria, the bacterial density of the aqueous suspension added to the contaminated medium being treated depends on the concentration of the hydrocarbon containing composition added to the contaminated medium. In one preferred embodiment, the bacterial density of the aqueous suspension ranges from 1 cell / L to 10 ⁸ cells / L, more preferably from 10 ² cells / L to 10 ⁶ cells / L, most preferably Preferably in the range of 10 ⁴ cells / L to 10 ⁵ cells / L.

Such aqueous suspensions comprising microorganisms may be sprayed onto the surface of the composite material comprising the surface treated calcium carbonate and the hydrocarbon containing composition and / or the composite comprising the calcium carbonate and hydrocarbon containing composition surface treated by a suitable pumping means. It can be injected into a contaminated medium containing the substance. Depending on the selected one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition, the growth of the microorganisms added to the contaminated medium may result in a sufficient amount of key nutrients such as phosphate, ammonium nitrate, protein, alkali metal ammonium phosphate, glucose And may be supported by spraying and / or injecting dextrose, urea, yeast, and the like. Such nutrients may be added to the aqueous suspension containing the microorganisms. Additionally or alternatively, the nutrients may be injected into and / or sprayed on the surface of the composite material in a separate aqueous suspension.

When the surface treated calcium carbonate is incorporated into the nonwoven, the nonwoven may be further treated with the aqueous suspension comprising microorganisms such that an aqueous suspension is sprayed onto the nonwoven and / or injected into the nonwoven. Optionally, nutrients may be sprayed onto the nonwoven and / or injected into the nonwoven as described above.

In one preferred embodiment of the invention, the composition comprising one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition comprises an amount of from 1 ppm to 10,000 ppm, preferably 250, calculated relative to the hydrocarbon-containing composition. It is added to a composite material comprising calcium carbonate and hydrocarbon containing compositions surface-treated in an amount from ppm to 5,000 ppm, most preferably from 500 ppm to 2,500 ppm.

The ratio of the surface treated calcium carbonate and the composition comprising one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition may vary over a wide range. In the composite material according to the invention, the ratio of the surface treated calcium carbonate and the microbial composition is preferably 10: 1 to 1:10, preferably 5: 1 to 1: 5, particularly preferably 2: 1. To a weight ratio of from 1: 2.

Compositions comprising one or more microorganisms capable of degrading one or more components of the hydrocarbon containing composition preferably comprise aerobic bacteria. If water is to be treated with a composition comprising at least one microorganism capable of breaking down at least one component of the hydrocarbon-containing composition, the oxygen content in the water is preferably at least 0.2 mg / l, more preferably at least 0.5 mg / l. Even more preferably at least 1 mg / l, most preferably at least 1.5 mg / l.

Examples of bacterial strains that may suitably be used in step d) of the method include Cyclobacter, Pseudomonas, Pseudobacterium, Axinebacter, Vibrio, Planococcus, Actinobacterium, Asrobacter, Marinobacter, Methyllosinus, methyllomonas, methyllobacterium, mycobacterium, nocardia, bacillus, brevibacterium, microcacus, corynebacterium, sarcina, streptomyces, flabobacterium, Xanthomonas and mixtures thereof.

In one particularly preferred embodiment, the composition comprising one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition comprises cyclobacter glacincola, acintobacter calcoaceticus, axinetobacter faecalis and Bacterial strains selected from the group comprising mixtures thereof.

Examples of fungal strains that may suitably be used in step d) of the method are Aspergillus plabus, Aspergillus pumigates, Aspergillus niger, Aspergillus nibeus, Aspergillus tereus, Aspergillus Russ Bercicola, Fusarium species, Mortierella species, Mucor, Mycelia, Penicillium corypilum, Pasilomyces nives, Pasilomyces varioti, Resophors, Talamoresis, Tricoder Horses and mixtures thereof.

Compositions comprising one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition used in step d) of the process of the invention preferably contain said hydrocarbons based on the total weight of the hydrocarbon-containing composition. At least 25%, preferably at least 40%, more preferably at least 50%, even more preferably at least 60%, most preferably at least 70% to the composition. In one particularly preferred embodiment, a composition comprising at least one microorganism capable of degrading at least one component of the hydrocarbon-containing composition used in step d) of the process of the invention is based on the total weight of the hydrocarbon-containing composition. At least 75% degradation for.

In one preferred embodiment, a composition comprising one or more microorganisms capable of decomposing one or more components of a hydrocarbon-containing composition comprises a mixture of two or more microorganisms capable of decomposing one or more components of a hydrocarbon-containing composition. Preferably, a composition comprising one or more microorganisms capable of decomposing one or more components of the hydrocarbon-containing composition comprises a mixture of three or more microorganisms capable of decomposing one or more components of the hydrocarbon-containing composition. Even more preferably, a composition comprising one or more microorganisms capable of degrading one or more components of a hydrocarbon-containing composition comprises a plurality of microorganisms capable of decomposing one or more components of a hydrocarbon-containing composition. If a composition comprising at least one microorganism capable of degrading at least one component of the hydrocarbon containing composition comprises a mixture of two or more microorganisms, one microorganism is preferably a bacterial strain of Cyclobacter glacincola.

In one particularly preferred embodiment, the surface treated calcium carbonate of step b) is further immobilized with one or more microorganisms that can degrade one or more components of the hydrocarbon-containing composition.

In one preferred embodiment, step c) and step d) are performed simultaneously. If steps c) and d) are carried out simultaneously, the composition comprising at least one microorganism capable of decomposing at least one component of the surface treated calcium carbonate and hydrocarbon containing composition of the invention is preferably in the form of a slurry Comes with. That is, the slurry includes not only the surface treated calcium carbonate of the present invention but also a composition comprising one or more microorganisms capable of decomposing one or more components of the hydrocarbon-containing composition.

Alternatively, steps c) and d) are performed separately. In this case, the hydrocarbon containing composition is first contacted with the surface treated calcium carbonate and then with the composition comprising one or more microorganisms capable of decomposing one or more components of the hydrocarbon containing composition.

In one preferred embodiment of the method of the invention, step c) or step d) is repeated one or more times. In a further preferred embodiment, step c) and step d) are repeated one or more times. If steps c) and d) are repeated one or more times, steps c) and d) may be repeated independently. That is, step c) can be repeated several times, while step d) is repeated more or less times than step c) (and vice versa). For example, step c) may be repeated twice, while step d) is repeated once or more than two times.

The use of surface treated calcium carbonate or methods of combining hydrocarbon containing compositions of the present invention provide a number of improved properties. First, the surface treated calcium carbonate of the present invention provides significant binding and biopurification activity when applied at least partially on the surface of the hydrocarbon containing composition or mixed with the hydrocarbon containing composition. Furthermore, the surface treated calcium carbonate of the present invention provides significant binding and biopurification activity when applied at least partially on the surface of the hydrocarbon containing composition and mixed with the hydrocarbon containing composition. Furthermore, the surface treated calcium carbonate of the present invention provides significant binding and biopurification activity when incorporated into nonwovens, such as biodegradable nonwovens and applied on the surface of hydrocarbon-containing compositions in the form of such nonwovens. . Preferably, the surface treated calcium carbonate of the present invention further comprises an aqueous suspension of one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition and / or capable of degrading one or more components of the hydrocarbon-containing composition. When immobilized with one or more microorganisms, it provides significant binding and biopurification activity when applied onto the surface of a hydrocarbon-containing composition.

The addition or use of the surface treated calcium carbonate of the present invention, or the method of the present invention, results in a composite material comprising a surface treated calcium carbonate and a hydrocarbon containing composition that can be easily removed from the contaminated medium being treated. Furthermore, the binding and biopurification of hydrocarbon-containing compositions with the surface treated calcium carbonate of the present invention results in an excellent cleaning quality of the treated medium.

Surface treated calcium carbonate can be stored for an indefinite period of time, not classified as a toxic product, and can be easily dispersed throughout the contaminated medium being treated. Furthermore, the surface treated calcium carbonate further comprises an aqueous suspension of one or more microorganisms capable of breaking down one or more components of the hydrocarbon-containing composition and / or immobilized with one or more microorganisms that can degrade one or more components of the hydrocarbon-containing composition. Silver enables not only efficient bonding of hydrocarbon containing compositions but also efficient biopurification of hydrocarbon containing compositions within a short time.

Depending on the specific requirements and / or the respective physical and / or chemical properties of the hydrocarbon-containing composition to be treated, one capable of decomposing the surface treated calcium carbonate and one or more components of the hydrocarbon-containing composition used in accordance with the process of the invention. Both compositions comprising the above microorganisms can be applied individually, or a finished mixture can be used. In the form of separately metering and adding individual components of a composition comprising one or more microorganisms capable of decomposing one or more components of the surface treated calcium carbonate and hydrocarbon containing composition, the concentration ratio is individually dependent upon the present contaminated medium being treated. Can be adjusted. Contaminated media can be treated with, for example, surface treated calcium carbonate that is formulated as a mixture into conventional formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and nonwovens.

A further advantage of the surface-treated calcium carbonate of the present invention or the process of the present invention lies in the fact that the surface-treated calcium carbonate used accelerates the biological recovery process of the hydrocarbon-containing composition without disturbing the ecological balance. Another advantage of the surface treated calcium carbonate of the present invention or the process of the present invention is that any of the components used, namely one or more microorganisms capable of decomposing one or more components of the surface treated calcium carbonate and / or hydrocarbon containing composition No subsequent contamination of the medium being treated. After use, their residual material already exists in the natural environment.

The most important application among soil, coastline, seawater, purified water or groundwater is the cleaning of accidentally distributed hydrocarbon containing compositions. In particular, oil spills affected by the release of crude oil from tankers, offshore structures, drilling rigs and oil wells, as well as heavy fuels used by refined petroleum products and large vessels, such as bunker fuels, or oily waste or The outflow of waste oil is considered an important application. Applications may also be possible for the cleaning of hydrocarbon contaminated media from different industries, such as the railway, airline and land transportation industries, as well as the oil storage, transportation, refining and fuel distribution industries. In this regard, cleaning of containers, reservoirs and all kinds of means for storage, transportation, refining and fuel distribution are considered important applications.

In view of the very good results of the surface treated calcium carbonate in the binding and biopurification of hydrocarbon-containing compositions from contaminated media as defined above, a further aspect of the present invention provides for binding and biopurification of hydrocarbon-containing compositions. It is the use of the said surface-treated calcium carbonate. According to another aspect of the invention, there is provided a composite material comprising a surface treated calcium carbonate and a hydrocarbon containing composition. With respect to the definition of surface treated calcium carbonate and / or hydrocarbon containing compositions and preferred embodiments thereof, the description provided above is mentioned when discussing the technical details of the surface treated calcium carbonate and / or hydrocarbon containing compositions.

The following examples may further illustrate the invention but are not intended to limit the invention to the illustrated embodiments. The following examples show good microbiological stability of aqueous formulations of minerals, pigments or fillers protected with the compositions according to the invention.

Example

How to measure

The following measurement methods were used to evaluate the parameters set forth in the examples and claims.

BET specific surface area of the material

After conditioning the sample by heating at 250 ° C. for 30 minutes, the BET specific surface area was measured using a BET method according to ISO 9277 using nitrogen. Prior to this measurement, the sample was filtered, rinsed and dried in an oven at 110 ° C. for at least 12 hours.

Particle size distribution (mass% particles with a diameter less than X) of the particulate matter and the weight average diameter (d ₅₀ )

The sedimentation method, ie the analysis of the sedimentation behavior in the gravitational field, determined the weight median particle diameter and particle diameter mass distribution of the particulate material. The measurements were performed using a Cedigraph ™ 5100.

Methods and apparatus are known to those skilled in the art and are commonly used to determine particle size of fillers and pigments. The measurement was carried out in an aqueous solution of 0.1 wt% Na ₄ P ₂ O ₇ . Samples were dispersed using a high-speed stirrer and ultrasonic waves.

Aerobic Decomposition

The measurement was performed according to the OECD 301 D closure test.

Anaerobic  decomposition

The measurement was performed according to OECD 311.

Anaerobic biodegradability measurement of organic compounds in chopped sludge was carried out as a measure of gas production.

Biological oxygen demand

BOD was evaluated as described in OECD 301D.

Analytical GC-MS

Samples were extracted with diethyl ether and analyzed on an AutoSystem XL Perkin Elmer according to the standard method of the RDS-ANA lab (report 58072.10).

Aliphatic carboxylic acid accessible surface area

Aliphatic carboxylic acid accessible surface areas can be measured by the methods described in Papirer, Schultz and Turchi, Eur.Polym. J., Vol. 20, No. 12, pp. 1155-1158, 1984.

Example 1

Illustrative examples below include the use of surface treated natural calcium carbonate powders for binding and biopurifying hydrocarbon containing compositions by measuring residual hydrocarbon compounds over a period of 60 days for aerobic and aerobic samples, respectively. The surface treated natural calcium carbonate powder had a weight median particle diameter d ₅₀ value of 1.4 μm (measured according to the sedimentation method) and a specific surface area of 5.5 m 2 / g (measured through the use of nitrogen and BET methods) prior to surface treatment. Has Surface treated natural calcium carbonate is coated with a coating comprising stearic acid and / or its reaction product. The reaction product of stearic acid and / or stearic acid is present in the coating in an amount of 0.7% by weight based on the dry weight of the calcium carbonate.

The aerobic and anaerobic biodegradation of crude oil in seawater was carried out using seawater sampled from a fjord close to the Omya Molde, Norway. 1000 ppm of crude oil was used and the precipitant was a surface treated natural calcium carbonate powder as described above. Surface treated natural calcium carbonate was used in the weight ratio of the surface treated calcium carbonate and the hydrocarbon containing composition of 10: 1. Biogas (BG) production for each of the aerobic and aerobic samples was monitored at 10 ° C. over a period of 60 days. Residual hydrocarbon compounds were measured by GC-MS. Table 1 summarizes the details of the bacterial strains used and the oil recovery measured.

Ultramicrobial bacteria were provided by UltraTech (USA) and are the longest registered biological / microbial products on EPA's National Emergency Product List for oil-borne water applications. Sludge samples were sampled from Arburg's plants. GC-MS profiles provide an indication of biopurified oil as compared to control samples without microorganisms. The reduction of about 30% hydrocarbons was determined by GC-MS during aerobic digestion in the presence of activated sludge and ultra-microorganisms, as well as in anaerobic samples inoculated with cut sludge. Thus, it can be concluded that bacterial oil degradation activity is provided during aerobic degradation.

Example 2

Illustrative examples below are surface treated natural calcium carbonate powders for binding and biopurifying hydrocarbon-containing compositions in seawater by measuring residual hydrocarbon compounds over a period of 60 days at a temperature of about 4 ° C. (see Example 1 above). Includes uses.

Aerobic biopurification of 100 ppm petroleum in seawater was carried out at 4 ° C. for a period of 60 days. Surface treated natural calcium carbonate was used in the weight ratio of the surface treated calcium carbonate and the hydrocarbon containing composition of 10: 1. Residual hydrocarbon compounds were measured by GC-MS. Table 2 summarizes the details of the bacteria used and the measured oil recovery.

During aerobic biopurification, about 78% to 13% of biopurification was obtained at 4 ° C. depending on the microorganism used. The combination of surface treated calcium carbonate and bacterial species Cyclobacter glassine cola (hydrolyzed bacterial strains isolated from extremely cold habitats) resulted in biopurification of up to 78% relative to the initial hydrocarbon concentration as measured by GC-MS. Achieved. Sewage samples from different plants were used to yield about 35% to 40% biopurification. In contrast, the microbes in the seabed sludge biocleanse only about 13% of the hydrocarbons, while the ultramicrobes did not show any biocleaning activity at 4 ° C. Thus, it can be concluded that bacterial oil degradation activity is provided during binding and aerobic biopurification.

Example 3

The following illustrative example shows a commercially available dispersant Corexit 9500 (Nalco®) for binding and biopurifying hydrocarbon-containing compositions in seawater by measuring residual hydrocarbon compounds at a temperature of about 4 ° C. over a period of 60 days. The use of surface treated natural calcium carbonate powder (see Example 1 above) in combination with Nalco (commercially available from USA). Furthermore, the residual hydrocarbon compounds measured over a period of 60 days at a temperature of about 4 ° C. for the surface treated natural calcium carbonate powder / Corexit 9500 combination are compared with the results obtained for the surface treated natural calcium carbonate powder.

Aerobic biopurification of crude oil in seawater was carried out using seawater containing a dispersant. 100 ppm of petroleum was used and the precipitant was a surface treated natural calcium carbonate powder as described above in combination with a commercially available dispersant Korexit 9500 (Nalco). Surface treated natural calcium carbonate was used in the weight ratio of the surface treated calcium carbonate and the hydrocarbon containing composition of 10: 1. Residual hydrocarbon compounds were measured by GC-MS. Table 3 summarizes the details of the bacteria used and the measured oil recovery.

Table 4 below summarizes the oil recovery for the surface treated natural calcium carbonate powder / Corexit 9500 combination compared to the results obtained for the surface treated natural calcium carbonate powder over a period of 60 days at a temperature of about 4 ° C. do.

Example 4

CaCO ₃  Determination of the viability of bacteria after immobilization on the bed

Pseudomonas species and Cyclobacter glassine cola were immobilized on CaCO ₃ and stored for 31 days at room temperature. After storage, bacterial viability was measured.

A portion (100 μl) (> 10 ⁹ CFU / mL PBS) of a suspension of Pseudomonas species and Cyclobacter glacincola was mixed with 100 μl of sterile PBS, 80% sterile glycerol, edible oil (rapeseed oil), and for the microorganism. Each was mixed separately with polyethylene glycol (Fluka Order No. 82280) used as solvent.

Natural heavy calcium carbonate was coated with stearic acid in amounts of 0.2%, 0.6% and 1.2% by weight. The BET specific surface area was 0.61 m 2 / g and the weight average size was 19.5 μm.

Each suspension of 200 μl of premixed bacteria was mixed with 4 g of stearic acid coated calcium carbonate sample. The sample was vortexed for 1 minute, stirred for 30 minutes on a Turbula-mixer and incubated at room temperature in a closed vial. After 3 days, 10 days and 31 days, 1 g of dry calcium carbonate powder with immobilized bacteria was used for the measurement of TVC (total survival count).

For this measurement, 1 g of powder was mixed with 9 ml of disruption buffer (10 mM Tris, pH 8.0 buffered in 0.9% saline) to desorb microorganisms from a white pigment powder sample. The suspension was shaken on vortex for 60 seconds at 2500 rpm before being placed on the rotary shaker for 30 minutes at 400 UpM (at room temperature).

100 μl samples of these formulations were plated on Tryptic-Soy-Agar (TSA) plates and incubated at 30 ° C. for up to 5 days. All operations should be performed under sterile conditions without telling.

All listed bacterial counts (total survival count (TVC) values expressed in cfu / ml) in the tables below were reported 5 days after plating (“Bestimmung von aeroben mesophilen Keimen”, Schweizerisches Lebensmittelbuch, chapter 56, section 7.01, edition of 1985, revised version of 1988).

Tables 5-7 below list the results for Pseudomonas species and Table 8 lists the results for Cyclobacter glacincola.

Colony growth was judged after 24 and 48 hours (3 days later [Table 5], Pseudomonas only 24 hours after the fast growing species). After 48 hours the results were the same as after 24 hours.

Cooking Oil: Less than 10 after 1 and 5 days of incubation of TSA. Since the cooking oil was not sterilized or microfiltered, a negative control was needed to exclude possible bacterial growth due to the microorganisms present in the cooking oil due to contamination.

The results well show that when microorganisms are immobilized on treated calcium carbonate, they can be stored for at least 31 days, without loss of growth, especially in both cooking oil and water / PBS.

Taken together, the use of dispersant Corexit 9500 in combination with surface treated calcium carbonate (Bacterial strain Cyclobacter glasine) showed biopurification of up to 34% petroleum (relative to the initial hydrocarbon concentration as measured by GC-MS). It can be concluded that there is no positive effect on the binding and biopurification efficiency of the coke. In contrast, the surface treated calcium carbonate of the present invention achieves up to 78% biopurification compared to the initial hydrocarbon concentration as measured by GC-MS. In this regard, it should be recognized that the dispersant correxite 9500 used in combination with the surface treated calcium carbonate also contains several organic compounds. Therefore, it should be assumed that excess oil foreign organic compounds will affect the biopurification of each petroleum compound by affecting the metabolic balance of the bacterial strains used.

Claims (25)

Surface-treated calcium carbonate for bonding and bioremediating hydrocarbon-containing compositions having a decomposition rate for hydrocarbon-containing compositions that is at least 25% based on the total weight of the hydrocarbon-containing composition, calcium carbonate And at least 10% of the aliphatic carboxylic acid accessible surface area of is coated by a coating comprising at least one aliphatic carboxylic acid having from 5 to 24 carbon atoms and / or a reaction product thereof. The surface-treated calcium carbonate comprises ground calcium carbonate and / or precipitated calcium carbonate and / or surface-modified calcium carbonate, preferably heavy calcium carbonate. Surface-treated calcium carbonate. The source of heavy calcium carbonate (GCC) is selected from marble, chalk, calcite, dolomite, limestone and mixtures thereof, and / or hard calcium carbonate (PCC) is a mineral of aragonite, batterite and calcite. Surface-treated calcium carbonate selected from one or more of the crystalline forms. The surface treated calcium carbonate according to claim 1, wherein the surface treated calcium carbonate is from 0.1 μm to 250 μm, preferably from 1 μm to 200 μm, more preferably from 1 μm to 150 μm, even more preferably. Surface treated calcium carbonate having a weight median particle diameter d ₅₀ value of 1 μm to 100 μm, most preferably 3 μm to 100 μm. 5. The coating of claim 1, wherein the coating of the surface treated calcium carbonate is pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid. , Group consisting of myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosyl acid, behenic acid, tricosyl acid, lignoceric acid and mixtures thereof At least one aliphatic carboxylic acid selected from, preferably the aliphatic carboxylic acid is selected from the group consisting of octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and mixtures thereof , Most preferably the aliphatic carboxylic acid is selected from the group consisting of myristic acid, palmitic acid, stearic acid and mixtures thereof. The aliphatic carboxylic acid accessible surface area of calcium carbonate, preferably at least 30% of the accessible surface area and most preferably at least 50% of the accessible surface area of claim 1. Surface-treated calcium carbonate coated by a coating comprising at least one aliphatic carboxylic acid and / or reaction product thereof. The surface treated calcium carbonate of claim 1, wherein the surface treated calcium carbonate further comprises one or more microorganisms capable of decomposing one or more components of the hydrocarbon-containing composition. 8. The surface treated calcium carbonate of claim 7, wherein the surface treated calcium carbonate is immobilized with one or more microorganisms capable of degrading one or more components of the hydrocarbon containing composition. The surface treated calcium carbonate of claim 7 or 8, wherein the one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition are selected from one or more strains of bacteria and / or fungi. 10. The surface treated calcium carbonate of claim 9 wherein the one or more strains of bacteria and / or fungi is one or more strains of petroleum degraded bacteria and / or petroleum degraded fungi. 10. The method of claim 9 or claim 10 wherein the one or more strains of bacteria are bakteo (Psychrobacter), Pseudomonas (Pseudomonas), the shoe gambling Te Solarium (Pseudobacterium), evil cine Sat bakteo (Acinetobacter), Vibrio (Vibrio) into sayikeu, Playa no Rhodococcus (Planococcus), evil Martino tumefaciens (Actinobacterium), ahsseuro bakteo (Arthrobacter), Marino bakteo (Marinobacter), valerian (Methylosinus), Pseudomonas (Methylomonas), tumefaciens (Methylobacterium) methyl methyl when a methyl, MY M. Te Solarium (Mycobacterium), no carboxylic Dia (Nocardia), Bacillus (Bacillus), Brevibacterium (Brevibacterium), micro Rhodococcus (Micrococcus), Corynebacterium (Corynebacterium), Sar or when (Sarcina), Streptomyces ( Streptomyces ), Flavobacterium , Xanthomonas and mixtures thereof, more preferably Psychrobact er glacincola ), Acinetobacter calcoaceticus ), Acinetobacter faecalis , and surface treated calcium carbonates selected from the group comprising mixtures thereof. The surface treated calcium carbonate of claim 1, wherein the surface treated calcium carbonate is in powder form and / or in granule form or slurry form. 13. The surface treated calcium carbonate according to any of claims 1 to 12, wherein the surface treated calcium carbonate is incorporated into the nonwoven and preferably incorporated into the biodegradable nonwoven. As a method of binding and biopurifying a hydrocarbon-containing composition,
a) providing a hydrocarbon containing composition;
b) providing one or more surface treated calcium carbonates according to any one of claims 1 to 13; And
c) contacting the hydrocarbon-containing composition of step a) with the surface-treated calcium carbonate of step b) to obtain a composite material comprising the surface-treated calcium carbonate and the hydrocarbon-containing composition.
≪ / RTI > The method of claim 14, wherein the hydrocarbon containing composition is a refined petroleum product selected from the group comprising crude oil and / or gasoline, diesel fuel, aviation fuel, hydraulic oil, kerosene and mixtures thereof. The process of claim 14 or 15, wherein step c) at least partially coats the surface of the hydrocarbon-containing composition of step a) with the surface treated calcium carbonate of step b) and / or covers the hydrocarbon-containing composition of step a). By mixing with the surface treated calcium carbonate of step b). 17. The process according to any one of claims 14 to 16, wherein step c) comprises a weight ratio of the hydrocarbon-containing composition and the surface treated calcium carbonate to 10: 1 to 1: 100, more preferably 1: 1 to 1:50, Even more preferably from 1: 1 to 1:25, most preferably from 1: 1 to 1:15. 18. The process according to any one of claims 14 to 17, wherein the composite material obtained in step c) is contacted with a composition comprising at least one microorganism capable of decomposing at least one component of the hydrocarbon-containing composition. How to further include. The method of claim 18, wherein the one or more microorganisms capable of degrading one or more components of the hydrocarbon-containing composition are selected from one or more strains of bacteria and / or fungi. The method of claim 19, wherein the one or more strains of bacteria are Cyclobacter, Pseudomonas, Pseudobacterium, Axinebacter, Vibrio, Planococcus, Actinobacterium, Aslobacter, Marinobacter, Methylosinus, Methylonomonas, Methylobacterium, Mycobacterium, Nocardia, Bacillus, Brevibacterium, Microcacus, Corynebacterium, Sarcina, Streptomyces, Flavobacterium, Xanthomonas and their And selected from the group comprising cyclobacter glacincola, axinetobacter calcoaceticus, axinebacter faecalis, and mixtures thereof. 21. The method of any one of claims 18-20, wherein step c) and step d) are performed simultaneously or separately. The method of claim 14, wherein step c) and / or step d) is repeated one or more times. Use of the surface treated calcium carbonate according to any one of claims 1 to 13 for bonding and biopurifying hydrocarbon-containing compositions. 24. The use according to claim 23, wherein the surface treated calcium carbonate is used in soil, seawater, groundwater, flat water, shoreline, containers and / or reservoirs. A composite material comprising the surface treated calcium carbonate and hydrocarbon containing composition according to claim 1.